CN114455866A - CaO-MgO-SiO for mine filling2-H2O-shaped cementing material and preparation method thereof - Google Patents
CaO-MgO-SiO for mine filling2-H2O-shaped cementing material and preparation method thereof Download PDFInfo
- Publication number
- CN114455866A CN114455866A CN202210013003.3A CN202210013003A CN114455866A CN 114455866 A CN114455866 A CN 114455866A CN 202210013003 A CN202210013003 A CN 202210013003A CN 114455866 A CN114455866 A CN 114455866A
- Authority
- CN
- China
- Prior art keywords
- sio
- mgo
- cao
- micro powder
- filling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/02—Phosphate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
The invention relates to CaO-MgO-SiO for mine filling2‑H2O-shaped cementing material and a preparation method thereof. The technical scheme is as follows: mixing 60-80 wt% of the pretreated iron tailing micro powder and 20-40 wt% of the pretreated phosphorus tailing micro powder to obtain a first mixture; adding silicon micropowder accounting for 5-10 wt% of the first mixture, 1-5 wt% of sodium hydroxide and 100-200 wt% of water into the first mixture, and mixing to obtain a second mixture; adjusting the pH value of the second mixture to 11-13, and magnetically stirring to obtain slurry; solid-liquid separation of the slurry, freezing and drying the separated solid, keeping the temperature at 800-1000 ℃ for 1-3 h, cooling along with the furnace, grinding to obtain the mineral filling materialCaO‑MgO‑SiO2‑H2And (3) O cementing material. The invention has the characteristics of high resource utilization rate, low production cost and simple process, the strength of the prepared product conforms to the specification of non-ferrous metal mining design Specification (GB 50771-2012), the bleeding rate of the filling slurry is low, and the additional value is high.
Description
Technical Field
The invention belongs to the technical field of cementing materials for mine filling. In particular to CaO-MgO-SiO for mine filling2-H2O-shaped cementing material and a preparation method thereof.
Background
The iron tailings are solid or powder waste which is discharged after the ore dressing and cannot be temporarily utilized, are main components of industrial solid waste, and mainly comprise oxides of iron, silicon, magnesium, calcium and aluminum; the phosphate tailings are low-grade phosphate ores and are subjected to beneficiation and enrichment P2O5Solid waste is generated. At present, the stacking amount of iron tailings and phosphorus tailings rises year by year, not only occupies a large amount of land, but also brings about serious vegetation damage, water source pollution and other environmental problems, and even has the risk of dam break. Therefore, the resource utilization of iron tailings and phosphorus tailings has attracted attention of those skilled in the art.
At present, the resource utilization of iron tailings mainly comprises the following aspects: (1) iron tailings are selected again; (2) filling iron tailings underground; (3) as building materials; (4) used as soil conditioner and trace element fertilizer; (5) and (4) reclaiming vegetation by utilizing iron tailings and the like. The resource utilization of the phosphate tailings mainly comprises the following aspects: (1) re-selecting phosphorus tailings; (2) filling the phosphorus tail mine; (3) as building materials; (4) used as soil conditioner and trace element fertilizer; (5) reclamation of vegetation from phosphate tailings, etc.
The two tailings are subjected to resource utilization, so that mine enterprises adopt a mine underground filling mode to greatly consume the tailings due to high production cost and low tailing resource utilization rate. The mine underground filling material comprises a cementing agent and filling aggregate, wherein the cementing agent is generally cement; the filling cost of the cement accounts for 70% of the total filling cost, so that the mine filling cost is too high, and the economic benefit of an enterprise is seriously influenced; the filling aggregate is generally classified tailings or full tailings, the average particle size of the full tailings is 52 mu m, and the particle size of the classified tailings is generally coarse fraction tailings larger than 75 mu m, so that a large amount of screened micro powder is accumulated and is difficult to use; when the whole tailing is filled, a large amount of cement needs to be consumed to ensure certain filling strength due to too much micro powder, poor grain size distribution and increase of cement cost, so that the reduction process of tailings is greatly limited, and a large amount of micro powder is accumulated.
Therefore, in order to solve the problem of tailing micro powder accumulation and reduce the filling cost of a mine, technical personnel carry out deep research and technical development:
for example, in the patent technology of "an iron tailing cemented filling method" (CN102562148A), iron tailings, a consolidation agent and water are mixed and uniformly stirred to form slurry, namely the mine cemented filling material, although the strength meets the specification in the nonferrous metal mining design specification (GB 50771-2012), the filling cost is not significantly reduced, the bleeding rate is high, the tailings serve as filling aggregates and are not converted into high value-added materials, so that the utilization rate of tailing micro-recycling sand is not high.
As another example, the patent technology of "a system and a method for filling paste in a metallic ore whole tailings classification area" (CN105317458A) classifies whole tailings into coarse and fine tailings, and non-cemented fills the coarse tailings into a stope with a large goaf and a high strength requirement; and (5) performing cemented filling on the fine-fraction tailings to a stope with a small goaf and low strength requirement. Although the utilization of fine-grained tailings is improved, a small amount of cement is still needed to provide early strength, and meanwhile, the fine-grained tailings only fill small goafs, so that the application of the fine-grained tailings to all goafs is limited; namely, although the filling cost is reduced, the production process is complex, and the consumption of fine-grade tailings cannot be greatly increased.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide CaO-MgO-SiO for mine filling, which has the advantages of high resource utilization rate of iron tailing micro powder and phosphorus tailing micro powder, low production cost and simple process2-H2Preparation method of O-type cementing material, and CaO-MgO-SiO prepared by method and used for mine filling2-H2O-shaped cementing materialThe strength of the material meets the specification of non-ferrous metal mining design Specifications (GB 50771-2012), the bleeding rate of the filling slurry is low, the mine filling cost can be effectively reduced, and the additional value is high.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
firstly, ball milling the iron tailing micro powder and the phosphorus tailing micro powder for 2-3 min by using a ball mill respectively, then heating to 800-1000 ℃ at the speed of 0.5-5 ℃/min respectively, and preserving heat for 90-120 min to obtain pretreated iron tailing micro powder and pretreated phosphorus tailing micro powder respectively.
Mixing 60-80 wt% of the pretreated iron tailing micro powder and 20-40 wt% of the pretreated phosphorus tailing micro powder to obtain a first mixture.
Adding 5-10 wt% of silica powder, 1-5 wt% of sodium hydroxide and 100-200 wt% of water into the first mixture, mixing to obtain a second mixture, adjusting the pH value of the second mixture to 11-13, and magnetically stirring at 40-100 ℃ for 4-10 hours to obtain slurry.
Thirdly, performing solid-liquid separation on the slurry, freezing the separated solid for 1-2 hours at the temperature of-60 to-30 ℃, and drying for 12-24 hours at the room temperature and the vacuum degree of 2-5 Pa to obtain CaO-MgO-SiO for filling the mine2-H2And O, a cementing material precursor.
Step four, filling the mine with CaO-MgO-SiO2-H2Placing the precursor of the O-cementing material in a high-temperature furnace, heating to 800-1000 ℃ at the speed of 0.5-5 ℃/min, preserving the heat for 1-3 h, cooling to room temperature along with the furnace, grinding to the granularity of less than or equal to 75 mu m, and preparing the CaO-MgO-SiO for filling the mine2-H2And (3) O cementing material.
The average particle size of the iron tailing micro powder is less than or equal to 75 mu m; SiO of iron tailing micro powder2The content is 30-40 wt%.
The average particle size of the phosphate tailing micro powder is less than or equal to 75 mu m; in the phosphate tailing micro powder: the CaO content is 30-40 wt%, and the MgO content is 20-30 wt%.
The average particle size of the silicon micro powder is less than or equal to 1 mu m; SiO of fine silica powder2The content is more than or equal to 98wt percent.
The rotating speed of the magnetic stirring is 400-500 r/min.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
the invention takes the iron tailing micro powder and the phosphorus tailing micro powder as main raw materials to prepare CaO-MgO-SiO for filling mines2-H2The O cementing material has high recycling rate. In the preparation process, the iron tailing micro powder and the phosphorus tailing micro powder are respectively ground and calcined and are uniformly mixed to obtain a first mixture; mixing and stirring the first mixture, the silicon micropowder, the sodium hydroxide and the water to obtain a second mixture; adjusting the pH value of the second mixture, and magnetically stirring to obtain slurry; filtering, freezing, drying, calcining at 800-1000 ℃, grinding to obtain CaO-MgO-SiO for filling mine2-H2The O-type cementing material has simple process and low preparation cost, and is suitable for batch production.
CaO-MgO-SiO for mine filling prepared by the invention2-H2The O-type cementing material has high resource utilization rate, simple process and low preparation cost, the compressive strength of the O-type cementing material meets the regulations of nonferrous metal mining design Specifications (GB 50771-2012) and the bleeding rate of filling slurry is low, and the reasons are as follows:
on one hand, the invention adopts the iron tailing micro powder and the phosphorus tailing micro powder as raw materials, the iron tailing micro powder and the phosphorus tailing micro powder are subjected to mechanical and high-temperature heat treatment, CaO and MgO with high activity exist in the phosphorus tailing micro powder after mechanical grinding and high-temperature treatment, and the CaO and the MgO with high activity exist in the phosphorus tailing micro powder after mechanical grinding and high-temperature treatment, and the high-activity SiO in the iron tailing micro powder and the silicon micro powder2And the calcium silicate hydrate and the magnesium silicate hydrate gel form a crystalline state with a compact network structure, and substances without gelling activity are cemented together, so that the compressive strength is improved.
On the other hand, the iron tailing micro powder is ground and calcined to lead SiO to be treated2The Si-O chemical bond is broken and recombined to improve SiO2The reactivity of (a); the addition of silicon micropowder can improve the high-activity SiO in the solution2Adding sodium hydroxide as alkali activator, extractingThe alkalinity of the high solution; OH in alkaline environment-Can lead SiO in the iron tailing micro powder2Dissolving; the hydration temperature of 40-100 ℃ can accelerate the SiO2With Ca in solution2+And Mg2+Improving CaO-SiO reaction2-H2O and MgO-SiO2-H2The reaction rate of the O system is high, so that hydrated calcium silicate and hydrated magnesium silicate gel are generated; simultaneously, the hydration temperature is increased to enable the gelled substance to have a higher crystalline state, the generated gel material is dried, then the material is calcined at the temperature of 800-1000 ℃, the crystalline state of hydrated calcium silicate and hydrated magnesium silicate is removed of structural water to generate calcium silicate and magnesium silicate phases, the calcium silicate and the magnesium silicate phases are ground again until the granularity is less than or equal to 75 mu m, and the CaO-MgO-SiO for filling the mine is prepared2-H2And (3) O cementing material. The grinding can increase the specific surface area and the reaction activity of the cementing material, is beneficial to forming high-density C-H-S (hydrated calcium silicate) and M-H-S (hydrated magnesium silicate) after the calcium silicate and the magnesium silicate are rehydrated, and water is used as a reactant to participate in the product in a large amount, thereby greatly reducing the bleeding rate of slurry. CaO-MgO-SiO for mine filling2-H2The O-gelled material can regenerate hydrated calcium silicate and hydrated magnesium silicate after being rehydrated, and the regenerated hydrated calcium silicate and hydrated magnesium silicate still present compact network structures. Can improve the compressive strength and has safe and reliable quality.
CaO-MgO-SiO for mine filling prepared according to the invention2-H2Preparing a sample according to the building mortar basic performance test method standard (JGJ/T70-2009) by using a mixture of an O cementing material, coarse fraction tailings and water in a mass ratio of 1 to (2.5-8) to (0.87-6.67), curing the prepared sample for 28 days, and measuring: the compressive strength is 6.77-15.04 MPa; the bleeding rate of the sample is 2.5-4.2%.
Therefore, the invention has the characteristics of high resource utilization rate of the iron tailing micro powder and the phosphorus tailing micro powder, low production cost and simple process, and the prepared CaO-MgO-SiO for mine filling2-H2The strength of the O-type cementing material meets the specification of non-ferrous metal mining design Specifications (GB 50771-2012), the bleeding rate of the filling slurry is low, the mine filling cost can be effectively reduced, and the additional value is high.
Detailed Description
The invention is further described with reference to specific embodiments, without limiting its scope.
In this embodiment:
the average particle size of the iron tailing micro powder is less than or equal to 75 mu m; SiO of iron tailing micro powder2The content is 30-40 wt%.
The average particle size of the phosphate tailing micro powder is less than or equal to 75 mu m; in the phosphate tailing micro powder: the CaO content is 30-40 wt%, and the MgO content is 20-30 wt%.
The average particle size of the silicon micro powder is less than or equal to 1 mu m; SiO of fine silica powder2The content is more than or equal to 98wt percent.
The detailed description is omitted in the embodiments.
Example 1
CaO-MgO-SiO for mine filling2-H2O-shaped cementing material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
firstly, ball milling the iron tailing micro powder and the phosphorus tailing micro powder for 2-2.5 min by using a ball mill respectively, then heating to 800-850 ℃ at the speed of 0.5-2 ℃/min respectively, and preserving heat for 90-100 min to obtain pretreated iron tailing micro powder and pretreated phosphorus tailing micro powder respectively.
Mixing 60-65 wt% of the pretreated iron tailing micro powder and 35-40 wt% of the pretreated phosphorus tailing micro powder to obtain a first mixture.
Adding 5-6.25 wt% of silica powder, 1-2 wt% of sodium hydroxide and 100-125 wt% of water into the first mixture, mixing to obtain a second mixture, adjusting the pH value of the second mixture to 11-11.5, and magnetically stirring for 4-5.5 hours at 40-55 ℃ to obtain slurry.
Thirdly, performing solid-liquid separation on the slurry, freezing the separated solid for 1-1.25 h at the temperature of-60 to-50 ℃, and drying for 12-15 h at the room temperature and the vacuum degree of 2-3 Pa to obtain CaO-MgO-SiO for filling the mine2-H2And O, a cementing material precursor.
Step four, filling the mine with the filling materialCaO-MgO-SiO2-H2Placing the precursor of the O-cementing material in a high-temperature furnace, heating to 800-850 ℃ at the speed of 0.5-2 ℃/min, preserving the heat for 1-1.5 h, cooling to room temperature along with the furnace, grinding to the granularity of less than or equal to 75 mu m, and preparing the CaO-MgO-SiO for filling the mine2-H2And (3) O cementing material.
The rotating speed of the magnetic stirring is 400-430 r/min.
CaO-MgO-SiO for mine filling produced in this example2-H2Preparing a sample according to the standard of building mortar basic performance test method standard (JGJ/T70-2009), curing the prepared sample for 28 days, and measuring the mass ratio of the O cementing material to the coarse fraction tailings to water of 1 to (0.125-0.200) to (2.5-6.7): the compressive strength is 6.77-11.70 MPa; the bleeding rate of the sample is 2.50-3.52%.
Example 2
CaO-MgO-SiO for mine filling2-H2O-shaped cementing material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
firstly, ball milling the iron tailing micro powder and the phosphorus tailing micro powder for 2-2.5 min by using a ball mill respectively, then heating to 850-900 ℃ at the speed of 2-3 ℃/min respectively, and preserving heat for 100-110 min to obtain pretreated iron tailing micro powder and pretreated phosphorus tailing micro powder respectively.
Mixing 65-70 wt% of the pretreated iron tailing micro powder and 30-35 wt% of the pretreated phosphorus tailing micro powder to obtain a first mixture.
Adding silicon powder accounting for 6.25-7.50 wt% of the first mixture, 2-3 wt% of sodium hydroxide and 125-150 wt% of water into the first mixture, mixing to obtain a second mixture, adjusting the pH value of the second mixture to 11.5-12, and magnetically stirring for 5.5-7 hours at 55-70 ℃ to obtain slurry.
Thirdly, performing solid-liquid separation on the slurry, freezing the separated solid for 1.25 to 1.5 hours at the temperature of between 50 ℃ below zero and 40 ℃ below zero, and drying the solid for 15 to 18 hours at the room temperature and the vacuum degree of 3 to 4Pa to obtain the CaO-MgO-SiO for filling the mine2-H2And O, a cementing material precursor.
Step four, filling the mine with CaO-MgO-SiO2-H2Placing the precursor of the O-cementing material in a high-temperature furnace, heating to 850-900 ℃ at the speed of 2-3 ℃/min, preserving the heat for 1.5-2 h, cooling to room temperature along with the furnace, grinding to the granularity of less than or equal to 75 mu m, and preparing the CaO-MgO-SiO for filling the mine2-H2And (3) O cementing material.
The rotating speed of the magnetic stirring is 430-450 r/min.
CaO-MgO-SiO for mine filling produced in this example2-H2Preparing a material with the mass ratio of the O-gelled material to the coarse fraction tailings to the water of 1 to (3.85-5) to (1.54-2.5), preparing a sample according to the standard of basic performance test method standard of building mortar (JGJ/T70-2009), curing the prepared sample for 28 days, and measuring: the compressive strength is 7.91-12.95 MPa; the bleeding rate of the sample is 2.70-3.79%.
Example 3
CaO-MgO-SiO for mine filling2-H2O-shaped cementing material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
firstly, ball milling the iron tailing micro powder and the phosphorus tailing micro powder for 2.5-3 min by using a ball mill respectively, then heating to 900-950 ℃ at the speed of 3-4 ℃/min respectively, and preserving heat for 110-115 min to obtain pretreated iron tailing micro powder and pretreated phosphorus tailing micro powder respectively.
And mixing 70-75 wt% of the pretreated iron tailing micro powder and 25-30 wt% of the pretreated phosphorus tailing micro powder to obtain a first mixture.
And secondly, adding 7.50-8.75 wt% of silica powder, 3-4 wt% of sodium hydroxide and 150-175 wt% of water into the first mixture, mixing to obtain a second mixture, adjusting the pH value of the second mixture to 12-12.5, and magnetically stirring for 7-8.5 hours at 70-85 ℃ to obtain slurry.
Thirdly, performing solid-liquid separation on the slurry, freezing the separated solid for 1.5 to 1.75 hours at the temperature of between 40 ℃ below zero and 35 ℃ below zero, and drying the solid for 18 to 21 hours at the room temperature and the vacuum degree of 4 to 5Pa to obtain the CaO-MgO-SiO for filling the mine2-H2And O, a cementing material precursor.
Fourthly, filling the mine with CaO-MgO-SiO2-H2Placing the precursor of the O-cementing material in a high-temperature furnace, heating to 900-950 ℃ at the speed of 3-4 ℃/min, preserving the heat for 2-2.5 h, cooling to room temperature along with the furnace, grinding to the granularity of less than or equal to 75 mu m, and preparing the CaO-MgO-SiO for filling the mine2-H2And (3) O cementing material.
The rotating speed of the magnetic stirring is 450-480 r/min.
CaO-MgO-SiO for mine filling produced according to this example2-H2Preparing a sample according to the standard of building mortar basic performance test method standard (JGJ/T70-2009), curing the prepared sample for 28 days, and measuring that the mass ratio of the O cementing material to the coarse fraction tailings to the water is 1 to (3.03-3.85) to (1.11-1.54): the compressive strength is 9.12-14.01 MPa; the bleeding rate of the sample is 3.05-4.01%.
Example 4
CaO-MgO-SiO for mine filling2-H2O-shaped cementing material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
firstly, ball milling the iron tailing micro powder and the phosphorus tailing micro powder for 2.5-3 min by using a ball mill respectively, then heating to 950-1000 ℃ at the speed of 4-5 ℃/min respectively, and preserving heat for 115-120 min to obtain pretreated iron tailing micro powder and pretreated phosphorus tailing micro powder respectively.
Mixing 75-80 wt% of the pretreated iron tailing micro powder and 20-25 wt% of the pretreated phosphorus tailing micro powder to obtain a first mixture.
Adding silicon powder accounting for 8.75-10 wt% of the first mixture, sodium hydroxide accounting for 4-5 wt% of the first mixture and water accounting for 175-200 wt% of the first mixture, mixing to obtain a second mixture, adjusting the pH value of the second mixture to 12.5-13, and magnetically stirring for 8.5-10 hours at 85-100 ℃ to obtain slurry.
Thirdly, performing solid-liquid separation on the slurry, freezing the separated solid for 1.75-2 h at the temperature of-35 to-30 ℃, and drying for 21-24 h at the room temperature and the vacuum degree of 4-5 Pa to obtain CaO-MgO-SiO for filling the mine2-H2And O, a cementing material precursor.
Step four, filling the mine with CaO-MgO-SiO2-H2Placing the precursor of the O-cementing material in a high-temperature furnace, heating to 950-1000 ℃ at the speed of 4-5 ℃/min, preserving heat for 2.5-3 h, cooling to room temperature along with the furnace, grinding to the granularity of less than or equal to 75 mu m, and preparing the CaO-MgO-SiO for filling the mine2-H2And (3) O cementing material.
The rotating speed of the magnetic stirring is 480-500 r/min.
CaO-MgO-SiO for mine filling produced in this example2-H2Preparing a sample according to the standard of building mortar basic performance test method standard (JGJ/T70-2009), curing the prepared sample for 28 days, and measuring the mass ratio of the O cementing material to the coarse fraction tailings to water of 1 to (3.5-3.03) to (0.87-1.11): the compressive strength is 10.28-15.04 MPa; the bleeding rate of the sample is 3.23-4.20%.
Compared with the prior art, the specific implementation mode has the following positive effects:
the specific embodiment takes the iron tailing micro powder and the phosphorus tailing micro powder as main raw materials to prepare CaO-MgO-SiO for filling the mine2-H2The O cementing material has high recycling rate. In the process of the re-preparation, the iron tailing micro powder and the phosphorus tailing micro powder are respectively ground and calcined and are uniformly mixed to obtain a first mixture; mixing the first mixture, the silicon micropowder, the sodium hydroxide and the water, and stirring to obtain a second mixture; adjusting the pH value of the second mixture, and magnetically stirring to obtain slurry; filtering, freezing, drying, calcining at 800-1000 ℃, grinding to obtain CaO-MgO-SiO for filling mine2-H2The O-type cementing material has simple process and low preparation cost, and is suitable for batch production.
CaO-MgO-SiO for mine filling prepared by the embodiment2-H2The O-type cementing material has high resource utilization rate, simple process and low preparation cost, the compressive strength of the O-type cementing material meets the regulations of nonferrous metal mining design Specifications (GB 50771-2012) and the bleeding rate of filling slurry is low, and the reasons are as follows:
on one hand, the specific embodiment adopts the iron tailing micro powder and the phosphorus tailing micro powderThe iron tailing micro powder and the phosphorus tailing micro powder are subjected to mechanical and high-temperature heat treatment as raw materials, CaO and MgO with high activity exist in the phosphorus tailing micro powder after mechanical grinding and high-temperature treatment, and the CaO and the MgO with high activity exist in the phosphorus tailing micro powder and the phosphorus tailing micro powder2And the calcium silicate hydrate and the magnesium silicate hydrate gel form a crystalline state with a compact network structure, and substances without gelling activity are cemented together, so that the compressive strength is improved.
On the other hand, the iron tailing micro powder is ground and calcined to lead SiO to be treated2The Si-O chemical bond is broken and recombined to improve SiO2The reactivity of (a); the addition of silicon micropowder can improve the high-activity SiO in the solution2Adding sodium hydroxide as an alkali activator to improve the alkalinity of the solution; OH in alkaline environment-Can lead SiO in the iron tailing micro powder2Dissolving; the hydration temperature of 40-100 ℃ can accelerate the SiO2With Ca in solution2+And Mg2+Improving CaO-SiO reaction2-H2O and MgO-SiO2-H2The reaction rate of the O system ensures that hydrated calcium silicate and hydrated magnesium silicate gel are generated; simultaneously, the hydration temperature is increased to enable the gelled substance to have a higher crystalline state, the generated gel material is dried, then the material is calcined at the temperature of 800-1000 ℃, the crystalline state of hydrated calcium silicate and hydrated magnesium silicate is removed of structural water to generate calcium silicate and magnesium silicate phases, the calcium silicate and the magnesium silicate phases are ground again until the granularity is less than or equal to 75 mu m, and the CaO-MgO-SiO for filling the mine is prepared2-H2And O, cementing materials. The grinding can increase the specific surface area and the reaction activity of the cementing material, is beneficial to forming high-density C-H-S (hydrated calcium silicate) and M-H-S (hydrated magnesium silicate) after the calcium silicate and the magnesium silicate are rehydrated, and water is used as a reactant to participate in the product in a large amount, thereby greatly reducing the bleeding rate of slurry. CaO-MgO-SiO for mine filling2-H2The O-gelled material can regenerate hydrated calcium silicate and hydrated magnesium silicate after being rehydrated, and the regenerated hydrated calcium silicate and hydrated magnesium silicate still present compact network structures. Can improve the compressive strength and has safe and reliable quality.
CaO-MgO-SiO for mine filling prepared according to the embodiment2-H2Preparing a sample according to the building mortar basic performance test method standard (JGJ/T70-2009) by using a mixture of an O cementing material, coarse fraction tailings and water in a mass ratio of 1 to (2.5-8) to (0.87-6.67), curing the prepared sample for 28 days, and measuring: the compressive strength is 6.77-15.04 MPa; the bleeding rate of the sample is 2.5-4.2%.
Therefore, the concrete implementation has the characteristics of high resource utilization rate of the iron tailing micro powder and the phosphorus tailing micro powder, low production cost and simple process, and the prepared CaO-MgO-SiO for mine filling2-H2The strength of the O-type cementing material meets the specification of non-ferrous metal mining design Specifications (GB 50771-2012), the bleeding rate of the filling slurry is low, the mine filling cost can be effectively reduced, and the additional value is high.
Claims (6)
1. CaO-MgO-SiO for mine filling2-H2The preparation method of the O-shaped cementing material is characterized by comprising the following steps:
firstly, ball-milling iron tailing micro powder and phosphorus tailing micro powder for 2-3 min by using a ball mill respectively, heating to 800-1000 ℃ at the speed of 0.5-5 ℃/min respectively, and preserving heat for 90-120 min to obtain pretreated iron tailing micro powder and pretreated phosphorus tailing micro powder respectively;
mixing 60-80 wt% of the pretreated iron tailing micro powder and 20-40 wt% of the pretreated phosphorus tailing micro powder to obtain a first mixture;
adding 5-10 wt% of silica powder, 1-5 wt% of sodium hydroxide and 100-200 wt% of water into the first mixture, mixing to obtain a second mixture, adjusting the pH value of the second mixture to 11-13, and magnetically stirring at 40-100 ℃ for 4-10 hours to obtain slurry;
thirdly, performing solid-liquid separation on the slurry, freezing the separated solid for 1-2 hours at the temperature of-60 to-30 ℃, and drying for 12-24 hours at the room temperature and the vacuum degree of 2-5 Pa to obtain CaO-MgO-SiO for filling the mine2-H2O cementing material precursor;
step four, filling the mine with CaO-MgO-SiO2-H2Placing the precursor of the O-cementing material in a high-temperature furnace, heating to 800-1000 ℃ at the speed of 0.5-5 ℃/min, preserving the heat for 1-3 h, cooling to room temperature along with the furnace, grinding to the granularity of less than or equal to 75 mu m, and preparing the CaO-MgO-SiO for mine filling2-H2And (3) O cementing material.
2. The mine filling CaO-MgO-SiO according to claim 12-H2The preparation method of the O-shaped cementing material is characterized in that the average particle size of the iron tailing micro powder is less than or equal to 75 mu m; SiO of iron tailing micro powder2The content is 30-40 wt%.
3. The mine filling CaO-MgO-SiO according to claim 12-H2The preparation method of the O-shaped cementing material is characterized in that the average particle size of the phosphate tailing micro powder is less than or equal to 75 mu m; in the phosphate tailing micro powder: the CaO content is 30-40 wt%, and the MgO content is 20-30 wt%.
4. The mine filling CaO-MgO-SiO according to claim 12-H2The preparation method of the O-shaped cementing material is characterized in that the average grain size of the silicon micro powder is less than or equal to 1 mu m; SiO of fine silica powder2The content is more than or equal to 98wt percent.
5. The mine filling CaO-MgO-SiO according to claim 12-H2The preparation method of the O-shaped cementing material is characterized in that the rotating speed of magnetic stirring is 400-500 r/min.
6. CaO-MgO-SiO for mine filling2-H2The O-type cementing material is characterized in that the CaO-MgO-SiO for filling the mine2-H2The O-type binder is CaO-MgO-SiO for mine filling according to any one of claims 1 to 52-H2CaO-MgO-SiO for mine filling prepared by preparation method of O cementing material2-H2And (3) O cementing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210013003.3A CN114455866B (en) | 2022-01-07 | 2022-01-07 | CaO-MgO-SiO for mine filling 2 -H 2 O-shaped cementing material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210013003.3A CN114455866B (en) | 2022-01-07 | 2022-01-07 | CaO-MgO-SiO for mine filling 2 -H 2 O-shaped cementing material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114455866A true CN114455866A (en) | 2022-05-10 |
| CN114455866B CN114455866B (en) | 2022-11-18 |
Family
ID=81409457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210013003.3A Active CN114455866B (en) | 2022-01-07 | 2022-01-07 | CaO-MgO-SiO for mine filling 2 -H 2 O-shaped cementing material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114455866B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115057638A (en) * | 2022-06-29 | 2022-09-16 | 武汉科技大学 | Calcium silicate hydrate and magnesium silicate hydrate gel material for mine filling and preparation method thereof |
| CN115872682A (en) * | 2022-12-26 | 2023-03-31 | 安徽马钢嘉华新型建材有限公司 | Preparation method of cementing material for high-sulfur tailing cemented filling |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424275A (en) * | 2003-01-10 | 2003-06-18 | 中国矿业大学（北京校区） | Cementing materials for filling, slurry and preparing and filling processes |
| CN104446045A (en) * | 2014-11-05 | 2015-03-25 | 武汉理工大学 | Alkali-activated cementing material and preparation method thereof |
| CN111196708A (en) * | 2020-01-10 | 2020-05-26 | 安徽马钢嘉华新型建材有限公司 | Mine underground filling mortar |
| CN112094063A (en) * | 2020-11-02 | 2020-12-18 | 长沙理工大学 | Wet-grinding tailing-based mine filling cementing material and preparation method and application thereof |
| CN112723804A (en) * | 2021-02-01 | 2021-04-30 | 东北大学 | High-silicon iron tailing cementing material and preparation method thereof |
| CN113200698A (en) * | 2021-05-24 | 2021-08-03 | 河北科技大学 | Preparation method of early strength additive for solid waste based cementing material |
-
2022
- 2022-01-07 CN CN202210013003.3A patent/CN114455866B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424275A (en) * | 2003-01-10 | 2003-06-18 | 中国矿业大学（北京校区） | Cementing materials for filling, slurry and preparing and filling processes |
| CN104446045A (en) * | 2014-11-05 | 2015-03-25 | 武汉理工大学 | Alkali-activated cementing material and preparation method thereof |
| CN111196708A (en) * | 2020-01-10 | 2020-05-26 | 安徽马钢嘉华新型建材有限公司 | Mine underground filling mortar |
| CN112094063A (en) * | 2020-11-02 | 2020-12-18 | 长沙理工大学 | Wet-grinding tailing-based mine filling cementing material and preparation method and application thereof |
| CN112723804A (en) * | 2021-02-01 | 2021-04-30 | 东北大学 | High-silicon iron tailing cementing material and preparation method thereof |
| CN113200698A (en) * | 2021-05-24 | 2021-08-03 | 河北科技大学 | Preparation method of early strength additive for solid waste based cementing material |
Non-Patent Citations (1)
| Title |
|---|
| 黄洋: "磷尾矿材料化综合利用途径研究进展", 《材料导报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115057638A (en) * | 2022-06-29 | 2022-09-16 | 武汉科技大学 | Calcium silicate hydrate and magnesium silicate hydrate gel material for mine filling and preparation method thereof |
| CN115872682A (en) * | 2022-12-26 | 2023-03-31 | 安徽马钢嘉华新型建材有限公司 | Preparation method of cementing material for high-sulfur tailing cemented filling |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114455866B (en) | 2022-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114455866B (en) | CaO-MgO-SiO for mine filling 2 -H 2 O-shaped cementing material and preparation method thereof | |
| CN102562148B (en) | Iron tailings cementing-filling method | |
| CN110104998B (en) | Micro-fine particle high-silicon tailing grouting material | |
| CN111689753B (en) | Gangue paste cementing material and preparation method thereof, gangue paste filling material and preparation method thereof | |
| CN110330243A (en) | A kind of no first-hand datum tailing filling novel gelled material | |
| CN111187045B (en) | Mine underground filling mortar prepared from steel slag sand and mineral processing waste | |
| CN113213787B (en) | Production process for preparing alkali cementing material from coal gangue | |
| CN111574170B (en) | Underground goaf filling material and preparation method thereof | |
| CN112125543B (en) | Composite gel material prepared from bulk solid wastes and preparation method thereof | |
| CN114213046B (en) | Clinker-free coal ash composite cementing material, preparation method thereof and coal mine filling paste | |
| CN109336506B (en) | Curing agent with strong curing capability and use method thereof | |
| CN111191387B (en) | Phosphogypsum-based cementing material optimization method for improving filling roof contact rate | |
| CN113603442A (en) | Low-cost gypsum-based self-leveling material | |
| CN105541255B (en) | Copper ashes base Low-silica iron ore tailings filler and its preparation technology | |
| CN115286305A (en) | Soil cave or karst cave filling grouting material and preparation method thereof | |
| CN111233382A (en) | Filling material using mineral processing tailings and filling process thereof | |
| CN110776281B (en) | Regenerated powder composite mine cemented filling material and preparation method thereof | |
| CN102994742A (en) | Method for producing sintered pellets by using red mud | |
| CN111138098B (en) | Method for preparing high-performance cementing material from modified calcium-magnesium phosphate ore tailings | |
| CN114804672B (en) | Superfine iron tailing filling cementing material and preparation method thereof | |
| CN115368100A (en) | Preparation method of special cementing material for high-content regenerated gypsum micro-expansion road base | |
| CN111960754A (en) | Solid waste base grouting material for mine water disaster control roof filling effect and preparation method thereof | |
| CN112851286A (en) | Method for preparing underground cementing filling material by fully utilizing fine-grained gold tailings | |
| CN115057638B (en) | Hydrated calcium silicate and hydrated magnesium silicate cementing material for mine filling and preparation method thereof | |
| CN116573867B (en) | Low-activity copper smelting slag composite cementing material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |